Process of producing fast dyeings on fibrous materials



Patented June 15, 1943 UNITED STATES PATENT or PROCESS OF PRODUCING FAST DYEINGS ON FIBROUS MATERIALS Richard Huss, Frankfort-on-the-Main, Germany,

assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application February 7, 1941, Serial No. 377,848. In.v Germany February 22, 1940 11 Claims.

The present invention relates to a process of producing fast dyeings and to the dyed fiber obtained thereby.

I hate found that valuable dyeings of good properties of fastness may be' obtained on animal fibers and natural or artificial cellulose fibers as well as on mixtures of animal fibers with cellulose fibers, furthermore on structures from synthetic polyamide compounds of high molecular weight by applying to' the fiber secondary disazodyestufis of the following composition:

azo-compound in an alkaline medium with 2- acetylamino-5- hydroxynaphthalene 7 's1l1fonic acid,

the dyestufi components being selected in such a manner that the finished dyestufl contains at least two solubilizing groups, and developing the dyeings thus obtained with water-soluble diazocompounds containing atleast one nitro-group, but no sulfonic acid or carboxylic acid group.

The blue to black dyeings thus obtained are distinguished by good properties of fastness, especially by very good fastness to light and to decatizing On mixed fabrics from wool and natural or regenerated celluloses there are obtained, after developin dyeings the various fibers of which are very uniform as regards their shadeand intensity of color.

If the dyeings obtainable by the present invention are treated with agents yielding metal either before or after or simultaneously with the development with, the water-soluble diazo-compounds containing at least one nitro-group, but no sulfonic acid or carbqxylic acid group, dyeings are obtained which possess enhanced properties of fastness, partly a better fastness to wetproccssing, partly a better fastnessto light. As agents yielding metal there may, for instance, be used salts of aluminium, copper, cobalt, nickel, chromium, manganese and mixtures of these salts.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto. t I

l. 1 kilo of a mixed fiber consisting of 50 parts ,of wool and 50 parts of staple fiber from cupram- 'monium cellulose is treated for one hour at 95 C. in a bath containing in 30 liters of water 40 g ams of the azo-dyestuff obtainable by coupling diazotiz -d l-amino-S-hydroxynaphthalene-7-sulfonic aci-i in an acid medium with l-aminonaphalenc-7-sulfcnic acid, diazotizing' again the monoazo-dyestuff obtained and coupling this di- 10 grams of the condensation productiifrom 1 mol of octodecyl alcohol and 20 mols of ethylene oxide,

100 grams of ammonium sulfate and 600 grams of sodium sulfate.

The material is then allowed to stand for half an hour at a temperature slowly falling to C. and thereupon it is rinsed. The dyeing is then developed for half an hour in the cold in a solution containing in 30 liters of water:

30 grams of the diazonium borofluoride from 1- amino-2-methyl-4-nitrobenzene i 10 grams of the condensation product from 1 mol ofoctodecylalcohol and 20 mols of ethylene oxide 5 grams of glacial acetic acid and 100 grams of sodium acetate and rinsed again. There is obtained a black dyeing of very good properties of fastness, especially of very good fastness to decatizing and to light. By after-treating the dyeing obtained with potassium bichromate in the heat, somewhat deeper dyeings with enhanced properties of fastness-are obtained.

0n wool dyeings of similar properties are obtained. For the production of dyeings on cotton or regenerated cellulose an addition of ammonium sulfate to the dye-bath is not necessary.

2. 1 kilo of an artificial wool containing beside wool artificial silk staple fiber and cotton is dyed for one hour at C. in a solution containing in 30 liters of water 40 grams of the sodium salt of the azo-dyestuif obtainable by coupling diazotized 1-amino-5-hydroxynaphthalene-7-sulfonic acid with 1-aminonaphthalene-7-sulfonic acid, diazotizing again the monoazodyestuifs obtained and coupling this diazo-compound with z-acetylamino-8-hydroxynaphthalene-6-su1fonic acid,

10 grams of the condensation product from 1 mol of octodecyl alcohol and 20 mols of ethylene oxide grams of ammonium sulfate and 600 grams of sodium sulfate The material is allowed to stand for half an hour while the temperature decreases, rinsed and treated for half an hour in the cold in a bath containing in 30 liters of cold water It is then' rinsed mid and hot. A; black dyeing of very good properties of fastness is obtained which may be improved by a treatment at boiling temperature with a solution of 20 grams of sodium bichromate, 10 grams of glacial acetic acid and 10 grams of the condensation product from 1 mol of octodecyl alcohol and 20 mols of ethylene oxide in 30 liters of water.

3. 1 kilo of a mixed fabric consisting of 50 parts of wool and 50 parts of staple fiber from viscose is treated for one hour at 95 C. and thereupon for half an hour at a temperature falling to 80 C. in a bath containing in 30 liters of water 30 grams of the sodium salt of 'the amdyestufl obtainable by coupling diazotized 1- amino-5-hydroxynaphthalene-7-sulfonic acid in an acid medium with l-amino-2-inethoxy-5- methylbenzene, diazotizing' again this monoazodyestufi and coupling the diazo-compound obtained in an alkaline medium with l-benzoylamino-8-hydroxy-naphthalene-4-sulfonic acid,

10 grams of the condensation product from 1 mol The material is then rinsed, developed for half an hour in a fresh bath with 25 grams of the diazonium borofluoride. from 4- nitraniline 10 grams of the condensation product from 1 mol of octodecylalcohol and mols of ethylene oxide and 100 grams of sodium acetate in 30 liters of cold water treated at 45 C. for A; hour with a solution of 5 grams of the condensation product from 1 mol of octodecylalcohol and 20 mols of ethylene oxide and 80 cc. of an ammonia solution of per cent strength in liters of water, rinsed and dried. A black dyeing of very good fastness to decatizing, to perspiration and to light is obtained. If the mixed fabric contains cotton knops, these are covered.

4. Mixed yam consisting of 30 parts of staple fiber from viscose and '70 parts of wool is dyed for one hour at 95 C. with 2 per cent of the azodyestufl 1-amino-5-hydroxynaphthalene-7-sulfonic acid- 1-naphthylamino-7 sulfonicacid 2- (4'-hydroxy 5' carboxyphenylamino) 5 hydroxynaphthalene-7-sulfonic acid, 0.5 per cent of the condensation product from 1 mol of octodecylalcohol and 20 mols of ethylene oxide,

7 10 per cent of ammonium sulfate and 50 per cent of sodiumsulfate the proportion of the goods to the liquor being The material is cooled to 80 C., rinsed and developed for half an hour in the cold with slowly heated to C., kept at this temperature for half an hour, rinsed and after-treated for' one hour at 85 C. to 90 C. with 3 per cent of chromic chloride and 1 per cent of glacial acetic acid A blue-black dyeing of very good properties of fastness is obtained. If there is used diazotized 76 zoy-lamino) -8 hydroxynaphthalene 6 sulfonic 10 per cent of ammonium sulfate 50 per cent of sodium sulfate and 0.5 per cent of the condensation product from 20 mols of ethylene oxide and 1 mol of octodecylalcohol the proportion of the goods to the liquor being 1:30.

The material is cooled to about 80 C. in the course of about half an hour, rinsed and developed for half an hour at ordinary temperature with 1 per cent of diazotized 1-amino-4-nitrobenzene in the form of the hydrochloride 0.5 per cent of the condensation product from 20 mols of ethylene oxide and 1 mol of octodecylalcohol 10 per cent of sodium acetate and 2 per cent of copper sulfate.

Then it is slowly heated to about 0., treated for about A ,to one hour at this temperature and rinsed. A black dyeing of very good properties of fastness, especially of very good fastness to light is obtained.

By exchanging the diazo-compound from 1- aminoi-nitrobenzene for the diazo-compound from 1-amino-3-nitrobenzene or 1-amino-2- methyl-4-nitrobenzene; similar black shades are obtained. By using the dia'zo compound from l-amino-2-methyl-5-nitrobenzene or 1-amino-2- nitro-4-chlorobenzene blue-black dyeings of very good properties and very good evenness of all silk a're dyed for-one hour at 95? C. on a winch dye beck with 2 per cent of the azo-dyestufi l-amino-S-hydroxynaphthalene-7-sulfonic acid- 2-amino-4- methylphenoxy acetic acid 2-(4'-hydroxy-3'- carboxyphenylamino) -5-hydroxynaphthalene 7-sulfonic acid 0.5 per cent of the condensation product from 20 mols of ethylene oxide and 1 mol of octodecylalcohol 10 per cent of ammonium sulfate and 50 per cent of sodium sulfate the proportion of the goods to the liquor being 1:30. The whole is then cooled to about 80 0., rinsed-and developed for half an hour in the cold with slowly heated to 45 0., further treated at this 4 per cent of the azo-dye'stufi temperature for about one hour and rinsed. A fast vivid navy-blue dyeing containing white effacts from acetate silk is obtained. By exchanging the diazotized 1-amino-3-nitro-6-niethylbenzene for. the'same quantity of diazotized 1- amino-3.nitrobe'nzene, a somewhat more covered shade is obtained.

7. Mixed yarn consisting of 50 parts of wool and 50 parts ofstaple fiber from viscose is dyed for one hour at 95 C. with The material is cooled to 80 C., rinsed and developed, first for .half an hour in the cold, then for half an hour at 45 C. with 1 per cent of diazotized 1-amino-4-nitrobenzene 25 0.5 per cent of the condensation product from 1 mol of octodecylalcohol and 20 mols of ethylene oxide and per cent of sodium acetate rinsed and treated for one hour at 90 C. with 2 30 per cent of potassium bichromate and 1 per cent of glacial acetic acid. A reddish black dyeing of good properties of i'astness is obtained.

Black dyeings of considerably enhanced fastness to light are obtained on mixtures of staple fiber from viscose and wool by developing a dyeing of 4 per cent of the azo-dyestufi 1-amino-5- hydroxynaphthalene-7-sulfonic acidzl-amino-2- methoxy -5- methylbenzene 1-benzoylamino-8- hydroxy'naphthalene-i-sulfonic acid with diazotized l-amino -2- methyl -4- nitrobenzene and after-treating the dyeing at C. with 2 per cent of copper acetate and l per cent of glacial acetic acid.

Dyeings of similar'iastness to light are obtained by developing a dyeing in the manner indicated in Example 5 of the before-mentioned azo-dyestufi on a mixture of staple fiber from viscose and wool with diazotized 1-amino-2-methyl-5-nitrobenzene,

0.5 per cent of the condensation product from 1 mol of octodecyl alcohol and 20 mols of ethylene oxide 2 10 per cent of sodium acetate 2 percent of copper sulfate and 2 per cent of chromic fluoride- The following table indicates the shades of a number or other dyeings obtainable by this invention: v

eve ope 71 e azocom- 00 ii an mx ers dycsmfl. pound fromfrom wool and artificial silk staple fiber l l-amino-5-hydroxynaphthalene-7-sulfonic acid l-aminn naphl-amin0-2-mcthyl-4-niro- Navy-blue.

thalenc-7-sulfonic acid 2-(4'-hydroxy-3-carhoxy-phenyl-amino)- benzene. 5-hydroxynaphthalene-7-sulfnnic acid.

2 1-amino-5-hydroxynaphthnlene-7-snlfonic acid l-amlno-naphthal-ainino-2-methoxy-4-nitrw Reddish black.

lene-7-sull'onic acid B-ureido-l-hydroxynaphthalene-3-sulionic benzene.

3 lamino5-hydroxynaphthalenc-7-snlionic acid -o--l-arninb-naphthal-amino-R-nitrobcnzene D0.

lenii-l-sugonic acid -a l-acetylamino-5-hydroxy-naphthalencJ-snb on cam 4 l-amino-5-hydroxynaphthalene-l-sulfonic acid l-amin'o-naphthal-amino-4-nitrobenzene Black.

" lenc-7-sult0nic acid -----a 2-(4'-met.hoxyphenylamino)-8-hydroxynaphthalene-t-sulfonie acid.

5 l-amino-5-hydroxynaphthalene-7-sulfonic acid ----0 l-amino aphtlial-ammo-3-nitrohenzene Blue-black.

Iene-7-sulionic acid H2, 4'-diehlorobenzoylamino)-8-hydroxyna hthaleno-4.6-disnlionic acid.

6 l-am no-5-hydroxynaphthaleneJ-sulionic acid-v l-amino-2-methoxyl-amino-2-met.hyl-4-nitro- Violet-tinged dark blue.

5-methylbenzene .2-(4-hydroxy-3'-carboxyphenylamino)-5-hybenzene.

' droxynaphthalene-7-sull'onic acid.

7 l-amino-5 hydi-oxynaphthalene-7-sulionic acid a lammo-2-mel-annno 2 methoxy 4 Reddish, blue-black.

thoxy-fi-methylbenzene l-(2'.4dichlorobenzoylamino)-8- nitrobcnzenc. hydroxynaphthaleneifi-disulfoiiic acid.

a l-amino-5-hydmxynaphthalene-7-sulfonic acid --0 l-ammo-S-methyll-amino-tl-nitrobenzene Violet-tinged black.

benzene l-acetyl-arnin0-R-hydroxynaphthaleneA-sulionie acid.

9 l-amino-5-hydroxy-naphthaleneJ-sulfonic acid. l-amino-2-mel-amino-2-nitro-4-methoxy- Blue-black.

10 do l-aunno-2-nitro-4-chleroben Do.

' zene. 1! ...do 1-amino-2-nitro-4-mcthyl- Do.

. benzene. v

12 .do... l-amino-2-nitrobenzene Do.

13 l-amino-5-hydroxynaphthalene-7-sulionic acid l-ammoM-diel-amino-4-nitrobenzene Reddish deep black.

thfiiicybenzene 2-acetylamino-S-hydroxynaphthalene-7-sulfonic I 14 l-amino'5-hydroxynaphthalene-7-snifonic acid 1-amino-2.5dil-amino-2-niiro-4-chiom Blnish black.

methoxybenzene 2-benzoylamino-8-hydroxynaphthalene-fibenzene. sulfonic acid.

15 do l-gemmo-ii-niixo-fi-meihyl- Reddish dark blue.

. nzene.

1R l-arnino-5-hydroxynaphlhalene-T-sulionic acid l-amino-naphtha- .....do Blue-black.

1ene-7-sulionic acid 1-butyrylainin:r8-hydroxy-naphthalene-i- I snllonic acid. f

17 l-an:ino-fi-hydroxynanhthalencJ-sulfonic acidi-ainlno-2-ethoxyi-amino-4-nitrohenzene Black.

naphthaiene-fi-sulfonic acid 2-acctylamino-8-hydroxynapbthalenc--6-sullonic acid.

18 l-amino-5-hydroxynaphthalene-7-sulfonic and i-aminmZ-cthoxydo Do.

. naphthalene-G-sulionic acid 2-acetylamino-E-hydroxynaphtalenn-7-sulfonic' acid.

19 l-amino 5-hydroxynaphthalene-7-sulionic acid -v l-amino-2.5-dil-amino-Ei-niiro-benzene.... Do.

methoxybenzene 2-(4'-aminoben:oylainmo)-8 hydroxynaphthalene-6-sulfonic acid. 1 I

2" l-amino-5-hydroxynaphthalene-7-sulionic acid 2-amino-4-methyll-amino-R-nitro-(i-methyl- Reddish navy-blue.

ydroxynaphthalenc-7-sulfonic acid.

21 i-amino 5-hydroxynaphthalene-7-sulfonic acid ---w l-aminoJi-sulfo-li-am1no-2-methyl-4-mim- Dark blue. nal ghtiioxy cetic acid 2-phenylamino-'thydzoi ynapiithaienefi' benzene. sn onic aei Shade of the] dye;- mg on woo co as simai'i g a g? reae W! are rom woo Pmmdwm and artificial silk staple fiber 22 l-amino--hydroxy-naphthalene-7-suli0nic acid Lamina-' 1-amino-2methyl- Copper suliate Black.

die:hosyb%izene Zphenylamino-S-hydroxynaphthalene-fi d nitrobenzene. su omc aci 23 1-emino-5-hydroxy-naphthaicne-7-sulionic acid 1-amino-2.5- 1-amino-3-uitro- ..do Do.

dlethoxy-benzone 2- henyl-amino-B-hydroxynapbthalene-G- benzene. sulionic acid.

24 Do l-amino-Z-meth- .do Do.

oxy-4-nitrobenzene.

25 1-amino-5-bydroxy-naphthalene-7-sulionic acid l-amino-2.5- l-amino-i-nitrodo Reddish black.

diethoxy-benzenc 2-acetylamine-5-hydroxynaphthalenc-7- benzene. suifonic acid.

26 Don... do Mixture oicopper Reddish black.

, sulfate and I chromic fluoride.

27 l-amino-s-hydroxy-naphtbalene-7-su1fonic acid l-amino-2.5- .do Coppersuliate Black.

dimethoxy-benzene Z-benzoylamino-8-hydt0xy-naphthalenefi-suii'onic acid; l I

28 i-amino-s-hydroxy-naphthalene-7-sullonic acid l-ammo-2.5- l-ammo-Z-meth- .do Reddish black.

dimethoxy-benzene 2-butyryl-amino-8-hydroxynaphthaieneyl 5 nitrobenfi-sulionic acid. zene.

29 l-amino-5-hydroxy-naphthalene-7-sulionic acid l-amino-2-ethoxy d0 do Black.

naphthalene-o-suiionic acid 2-acetyl-ammo-8-hydroxy-naphthalenc-G-sulfonic acid.

30 1-amino-5-hydroxy-naphthalene-7-snlfonic acid l-amino-G-sulfol-amino-2-methyl- .do Dark blue.

g-nalphtlioxygcetic acid 2-phenyl-ammo-5-hydroxynaphthalene- 4-nitrobenzene.

31 l-amino-5-hydroxynaphthalenc-7-sulf0nic acid l-aminonaph- .do Ami-treated with Reddish black.

thalene-7-sulfonic acid 1-acetylammo-5-hydroxynpathalene-7- Potassium bisulfonic acid. cbromate.

32 i-amino-5-hydroxynaphtl'ialeno-7-sulfonic acid l-aminonaphl-arnmo-2-methdo Black.

thaiene-7-sulfonic acid 1-(4'-methoxyphenylamino)-8 hydroxyoxy-4-nitrobennaphthalene-G-sulfonic acid. 'zenc.

33 l-amino-s-hydi-oxy-naphthalene-7-sulfonic and l-amino-2- l-amino-B-nitro- ..do Violet-tinged dark methoxyt-methylbenzene 2-(4-hydroxy-3'-carboxy-phenylbenzene. blue. amino)-5-hydroxynapbthaiene-7-sulfonic acid.

I claim: and naphthalene series being free from hydroxy wherein A means the radical of a 1-amino-5- hydroxynaphthalene, B the radical of an amine selected from the group consisting of the banzene and naphthalene series being free from hydroxy groups and coupled in para-position to the amino-group, C means the radical of an amino-hydroxynaphthalene sulfonic acid coupled on the naphthol side, X represents a member of the group consisting of hydrogen and alkyl and Y a member of the group consisting of an acyl and aryl radical, the dyestufif components being selected in such a manner that the finished dyestufi? contains at least two solubilizing groups, and developing the dyeings thus obtained with water-soluble diazo-compounds of the benzene series containing a nuclear nitro group, said diazo compounds being free from sulfonic acid and carboxylic acid groups.

2. A process of producing fast dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applying to the fiber secondary disazo-dyestufis of the following composition:

wherein A means the radical of a 1-amino-5- hydroxynaphthalene, B the radical of an amine selected from the group consisting of the benzene groups and coupled in para-position to the amino-group, C means the radical of an aminohydroxynaphthalene sulfonic acid coupled on the naphthol side, X represents a member of the group consisting of hydrogen and alkyl and Y a member of the group consisting of an acyl and aryl radical; the dyestufi components being selected in such a manner that the finished dyestufl contains at least two solubilizin groups, developing the dyeings thus obtained with watersoluble diazo-compounds of the benzene series containing a nuclear nitro-group, said diazo compounds bein free from sulfonic acid and carboxylic acid ,roups and treating them with agents yielding metal.

3. A process of producing fast blue-black dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applying to the fiber the secondary disazo-dyestufi 1-amino-5-hydroxynaphthalene- 7-sulfonic acid I-amino-Z-methoxy-5-methylbenzene 1-benzoylamino-8-hydroxynaphthalene-4-sulfonic acid and developing the dyeing thus obtained with the diazo-compound from a nitraniline.

' 4. A process of producing fast blue-black dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applying to the fiber the secondary 55 disazo-dyestufi 1-amino-5-hydroxynaphthalene- 7-su1fonic acid 1-amino-2-methoxy-5-methylbenzene 1-benzoylamino-8-hydroxynaphtha-' lene-4-sulfonic acid and developing the 'iyeing thus obtained with the diazo-compounu from l-aminoi-nitrobenzene.

5. A process of producing fast blue-black dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose 75 fibers by applying to the fiber the secondary disazo-dyestuii l-amino-5-hydroxynaphthalene- 7-sulionic acid l-amino-2-methoxy-5-methylbenzene l-benzoylamino-ii-hydroxynaphthalene-t-sulionic acid, developing the dyeing thus obtained with the diazo-compound from l-amino-4-nitrobenzene and treating it with an agent yielding metal.

6. A process of producing fast black dyeings on fibrous material of the group consisting of l-amino-i-nitrobenzene and treating itwith an agent yielding metal.

9. A process 01' producing vivid navy-blue dyeings on fibrous material 01' the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applyingto the fiber the secondary disazo-dyestufi. l-amino-S-hydroxynaphthaiene- 'l-sulionic acid 2-amino-4-methylphenoxy ace-' tic acid 2-(4'-hydroxy-3'-carboxyphenylamino) -5-hydroxynaphthalene-'7-sulionic acid and developing the dyeing thus obtained with the diazo-compound from a nitraniline. I

10. A process of producing vivid navy-blue dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose disazo-dyestufi 1-amino-5-hydroxynaphthalene- '7-sulfonic acid 1-amino-2.5-dimethoxybenzene 2-(4'-aminobenzoyiamino) -8-hydroxynaphthalene-G-sulionic acid and developing the dyeing thus obtained with the diam-compound from l-amino-d-nitrobenzene. A

8. A process of producingiast black dyeings on fibrous material of the group consisting of 3 animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applying to the fiber the secondary disazo-dyestufl l-aminb-S-hydroxynaphthalene- 'l-sulionic acid 1 amino 2.5 dimethoxybenzene 2 -(4'-aminobenzoylamino) 8 hydroxynaphthalene-G-sulionic acid, developing. the dyeing thus obtained with the diam-compound from fibers and mixtures of animal fibers with cellulose fibers by applyin to the fiber the secondary disazo-dyestuii 1-amino-5-hydroxynaphthalene- 'l-sulionic acid .2-amino-4-methylphenoxy acetic acid 2-(4-hydroxy-3'-carboxyphenylamino) -5-hydroxynapthalene 7 sulionic acid, and developing the dyeing thus obtained with the diam-compound from 1-amino-3-nitro-6- methylbenzene. 11. A process of producing vivid navy-blue dyeings on fibrous material of the group consisting of animal fibers, natural and artificial cellulose fibers and mixtures of animal fibers with cellulose fibers by applying to the fiber the secondary disazo-dyesmfl 1 amino 5 hydroxynaphthalene-'l-suiionic acid 2- amino-4- methylphenoxy acetic acid 2-(4'-hydroxy-3'- carboxyphenylamino) 5-hydroxynaphthalene-I- sulfonic acid, developing the dyeing thus obtained with the diam-compound from 1-amino-3.-nitrofi-methylbenzene and treating it yielding metal.

with an agent 

